This invention relates to novel tetrahydrofuran compounds useful as monomers to form base resins for use in chemically amplified resist compositions adapted for micropatterning lithography.
While a number of recent efforts are being made to achieve a finer pattern rule in the drive for higher integration and operating speeds in LSI devices, deep-ultraviolet lithography is thought to hold particular promise as the next generation in microfabrication technology. In particular, photolithography using a KrF or ArF excimer laser as the light source is strongly desired to reach the practical level as the micropatterning technique capable of achieving a feature size of 0.3 xcexcm or less.
The resist materials for use in photolithography using light of an excimer laser, especially ArF excimer laser having a wavelength of 193 nm, are, of course, required to have a high transmittance to light of that wavelength. In addition, they are required to have an etching resistance sufficient to allow for film thickness reduction, a high sensitivity sufficient to eliminate any extra burden on the expensive optical material, and especially, a high resolution sufficient to form a precise micropattern. To meet these requirements, it is crucial to develop a base resin having a high transparency, rigidity and reactivity. None of the currently available polymers satisfy all of these requirements. Practically acceptable resist materials are not yet available.
Known high transparency resins include copolymers of acrylic or methacrylic acid derivatives and polymers containing in the backbone an alicyclic compound derived from a norbornene derivative. All these resins are unsatisfactory. For example, copolymers of acrylic or methacrylic acid derivatives are relatively easy to increase reactivity in that highly reactive monomers can be introduced and acid labile units can be increased as desired, but difficult to increase rigidity because of their backbone structure. On the other hand, the polymers containing an alicyclic compound in the backbone have rigidity within the acceptable range, but are less reactive with acid than poly(meth)acrylate because of their backbone structure, and difficult to increase reactivity because of the low freedom of polymerization. Additionally, since the backbone is highly hydrophobic, these polymers are less adherent when applied to substrates. Therefore, some resist compositions which are formulated using these polymers as the base resin fail to withstand etching although they have satisfactory sensitivity and resolution. Some other resist compositions are highly resistant to etching, but have low sensitivity and low resolution below the practically acceptable level.
An object of the invention is to provide a novel tetrahydrofuran compound useful as a monomer to form a polymer for use in the formulation of a photoresist composition which exhibits firm adhesion and high transparency when processed by photolithography using light with a wavelength of less than 300 nm, especially ArF excimer laser light as the light source.
We have found that a tetrahydrofuran compound of formula (1), (2), (3) or (4) can be prepared in high yields by a simple method to be described later, that a polymer obtained from this tetrahydrofuran compound has high transparency at the exposure wavelength of an excimer laser, and that a resist composition comprising the polymer as a base resin is improved in adhesion to substrates.
The present invention provides a tetrahydrofuran compound of the following general formula (1). 
Herein the broken line represents a single bond, a divalent organic group, or a structure in which the alicyclic structure in the form of norbornene or tetracyclo[4.4.0.12,5.17,10]dodecene and the tetrahydrofuran cyclic structure share one or two constituent carbon atoms, and k is 0 or 1.
In one embodiment, the invention provides a tetrahydrofuran compound having the following general formula (2). 
Herein X is a single bond or a group xe2x80x94(CH2)mxe2x80x94 in which one or more methylene groups may be replaced by one or more oxygen atoms, m is an integer of 1 to 8, and k is 0 or 1.
Another embodiment is a tetrahydrofuran compound having the following general formula (3). 
Herein one of two Y""s is an oxygen atom and the other is a methylene group, and k is 0 or 1.
A further embodiment is a tetrahydrofuran compound having the following general formula (4): 
Herein one of two Z""s is an oxygen atom and the other is a methylene group, and k is 0 or 1.
The tetrahydrofuran compounds of the present invention have the general formula (1). 
Herein, the broken line represents a single bond, a divalent organic group, or a structure in which the alicyclic structure in the form of norbornene or tetracyclo[4.4.0.12,5.17,10]dodecene and the tetrahydrofuran cyclic structure share one or two constituent carbon atoms, and k is 0 or 1.
The divalent organic group is preferably a group xe2x80x94(CH2)mxe2x80x94 in which one or more methylene groups may be replaced by one or more oxygen atoms, wherein m is an integer of 1 to 8. Therefore, the preferred tetrahydrofuran compounds are those of the general formula (2). 
Herein X is a single bond or a group xe2x80x94(CH2)mxe2x80x94 in which one or more methylene groups may be replaced by one or more oxygen atoms, m is an integer of 1 to 8, and k is 0 or 1.
Those tetrahydrofuran compounds of the general formulae (3) and (4) are also preferred. 
Herein one of two Y""s is an oxygen atom and the other is a methylene group, and k is 0 or 1. 
Herein one of two Z""s is an oxygen atom and the other is a methylene group, and k is 0 or 1.
Illustrative examples of the inventive tetrahydrofuran compound are given below. 
It is believed that resist polymers obtained using these tetrahydrofuran compounds as the monomer exhibit good adhesion to substrates because the tetrahydrofuran moiety regarded as a polar group that brings out adhesion is positioned at a site separated apart from the polymer backbone by a linker such as an alkylene group. By selecting a tetrahydrofuran compound having a linker of optimum length and type as the monomer to form a polymer, the polymer as a whole can be adjusted to an appropriate lipophilicity and controlled in dissolution properties.
The tetrahydrofuran compounds of the invention can be produced by the following three methods, for example, but the invention is not limited to these methods.
The first method is synthesis by intramolecular dehydration/cyclization reaction of a corresponding diol compound (5). 
Herein the broken line and k are as defined above.
Better results are obtained from intramolecular dehydration reaction when an acid or a salt thereof, or a phosphorus reagent is used.
Examples of the acid used herein include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid and organic acids such as formic acid, acetic acid, benzoic acid, p-toluenesulfonic acid, and benzenesulfonic acid, and salts thereof as well as cation-exchange resins. Examples of the phosphorus reagent include hexamethylphosphoric triamide (HMPA), dialkyl azodicarboxylate-triphenylphosphine, triethylphosphine, and potassium carbonate-triphenylphosphine.
The second method involves the steps of converting a diol compound (5) to a compound (6) having a leaving group such as a halogen atom, alkylsulfonyloxy group or arylsulfonyloxy group, and treating the compound (6) with a base for cyclization into a tetrahydrofuran compound (1). 
Herein, X is a halogen atom, alkylsulfonyloxy group or arylsulfonyloxy group, and the broken line and k are as defined above.
The first step is to synthesize the compound (6) having a leaving group. Since the compound (5) has two primary hydroxyl groups in the molecule, only one of which should be converted to a leaving group X, the amounts of reagents and reaction conditions must be carefully determined.
In the case of the compound (6) having a leaving group X which is a halogen atom, X is preferably chlorine or bromine. In this case, various well-known methods are applicable to the synthesis of haloalcohol compound (6) from diol compound (5). Some exemplary methods use hydrohalogenic acids such as hydrochloric acid and hydrobromic acid, sulfur reagents such as thionyl chloride and thionyl bromide, and phosphorus reagents such as phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide or triphenylphosphine combined with various halogen sources.
In the case of the compound (6) having a leaving group X which is an alkylsulfonyloxy or arylsulfonyloxy group, X is preferably a methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy or p-toluenesulfonyloxy group for availability of their starting materials. In this case, the sulfonyloxy compound (6) is conventionally synthesized by reacting a corresponding sulfonyl halide with the diol compound (5) in a solvent in the presence of a base.
It is also possible to convert the compound (6) wherein X is an alkylsulfonyloxy or arylsulfonyloxy group to the haloalcohol compound (6) wherein X is halogen. In this case, reaction with a halide salt such as lithium chloride, lithium bromide, sodium bromide or calcium bromide may be carried out in a polar solvent such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or ethanol at room temperature or elevated temperature.
The second step is for a base to act on the compound (6) having a leaving group X in a solvent to produce the desired tetrahydrofuran compound. Examples of the base used herein include alkoxides such as sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, lithium tert-butoxide and potassium tert-butoxide; organic amines such as pyridine, triethylamine, N,N-dimethylaniline and 4-dimethylaminopyridine; inorganic hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide and tetra-n-butylammonium hydroxide; inorganic carbonates such as sodium carbonate, sodium hydrogen carbonate, lithium carbonate and potassium carbonate; alkyl metal compounds such as trityllithium, tritylsodium, tritylpotassium, methyllithium, phenyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium and ethyl magnesium bromide; and metal amides such as sodium amide, potassium amide, lithium diisopropylamide, potassium diisopropylamide, lithium dicyclohexylamide, potassium dicyclohexylamide, lithium 2,2,6,6-tetramethylpiperidine, lithium bistrimethylsilylamide, sodium bistrimethylsilylamide, potassium bistrimethylsilylamide, lithium isopropylcyclohexylamide and bromomagnesium diisopropylamide.
In the event where compound (6) is synthesized in the first step using a base, it can be further converted to compound (1) without isolation of the intermediate (6).
The third method is the synthesis of the desired tetrahydrofuran compound (2) from a tetrahydrofuran compound (7) and an alicyclic compound (8). 
Herein, X1 and X2 are groups which react with each other to form X, and X and k are as defined above.
X1 and X2 differ depending on the structure of X in the target compound. In one example wherein X1 and X2 are a haloalkyl group and an organometallic alkyl group, the compound (2) is synthesized through coupling reaction of these groups. In another example wherein X1 and X2 are a haloalkyl group and a hydroxyalkyl group, the compound (2) is synthesized through ether formation or O-alkylation reaction. One exemplary reaction scheme is shown below. 
Herein, X3 and X4 are halogen atoms, p is an integer of 1xe2x89xa6pxe2x89xa6m, and k and m are as defined above. In this process, either one of halide compounds (9) and (10) forms a Grignard reagent with magnesium, which undergoes coupling reaction with the other halide compound in the presence of a copper catalyst, yielding the tetrahydrofuran compound (11).
Another exemplary reaction scheme is shown below. 
Herein, one of X5 and X6 is a hydroxyl group and the other is a halogen atom, q and r are integers satisfying 1xe2x89xa6q+r+1xe2x89xa6m, and k and m are as defined above. In this process, compounds (12) and (13) are treated with a base to effect carbon-oxygen bond-forming reaction or etherification, yielding the desired tetrahydrofuran compound (14).
A polymer or high molecular weight compound is prepared using the inventive tetrahydrofuran compound as a monomer. The method is generally by mixing the monomer with a solvent, adding a catalyst or polymerization initiator, and effecting polymerization reaction while heating or cooling the system if necessary. This polymerization reaction can be effected in a conventional way. Exemplary polymerization processes are ring-opening metathesis polymerization, addition polymerization, and alternating copolymerization with maleic anhydride or maleimide. It is also possible to copolymerize the tetrahydrofuran compound with another norbornene monomer.
A resist composition is formulated using as a base resin the polymer resulting from polymerization of the tetrahydrofuran compound. Usually, the resist composition is formulated by adding an organic solvent and a photoacid generator to the polymer and if necessary, further adding a crosslinker, a basic compound, a dissolution inhibitor and other additives. Preparation of the resist composition can be effected in a conventional way.
The resist composition formulated using the polymer resulting from polymerization of the inventive tetrahydrofuran compound lends itself to micropatterning with electron beams or deep-UV rays since it is sensitive to high-energy radiation and has excellent sensitivity, resolution, and etching resistance. Especially because of the minimized absorption at the exposure wavelength of an ArF or KrF excimer laser and firm adhesion to the substrate, a finely defined pattern having sidewalls perpendicular to the substrate can easily be formed. The resist composition is thus suitable as micropatterning material for VLSI fabrication.